This application is a 371 of PTC/EP00/07632 filed Aug. 7, 2000. The present Application relates to novel formulations of fluorescent whitening agents and their use for the whitening of paper.
Fluorescent whitening agents of the formula 
in which
R1 is hydrogen, C1-C5-alkyl, C1-C5-alkoxy or halogen and
M is hydrogen, an alkali metal, preferably lithium, sodium or potassium, ammonium or magnesium, have long been known and are used, for example, for the whitening of paper materials.
These whitening agents are very sparingly soluble in water and are therefore usually commercially available in the form of slurries or of solutions which generally contain the sodium salt of the whitening agent and considerable amounts of a solubilizer, for example urea, or of an organic solvent, so that the whitening agent is completely dissolved. Since, after application, these solubilizers are undesired in the wastewater and moreover the organic solvents are generally flammable, there was a need for a formulation which contains no, or only small amounts of, such substances.
It has now been found that it is possible to prepare stable aqueous solutions of the fluorescent whitening agents of the abovementioned formula (1) if the whitening agents are dissolved in water together with a polyvinyl alcohol which may have been modified. Surprisingly, it is possible in this way to prepare solutions which contain up to 20% of whitening agent and have a shelf-life of several months at temperatures between 0 and 40xc2x0 C. The addition of polyvinyl alcohol furthermore enhances the whitening effect of the whitening agent when applied to the surface, so that less active substance is required in order to achieve the same effect.
The present invention thus relates to formulations of fluorescent whitening agents which contain
a) 2 to 20% by weight of a fluorescent whitening agent of the formula 
xe2x80x83in which
xe2x80x83R1 is hydrogen, C1-C5-alkyl, C1-C5-alkoxy or halogen and
xe2x80x83M is hydrogen, an alkali metal, ammonium or magnesium,
b) 4 to 30% by weight of an unmodified or modified polyvinyl alcohol,
c) 55 to 94% by weight of water and
d) 0 to 20% by weight of further additives.
M is hydrogen or one equivalent of a colourless cation, for example lithium, sodium, potassium, ammonium or the protonated form of a C4-C12-trialkylamine, C4-C12diamine, C2-C15ralkanolamine or polyglycolamine. Preferably, M is potassium or in particular sodium.
Alkyl R1 is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isoamyl or sec-amyl. If, in the formula (1), R1 is alkoxy, this is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamyloxy or sec-amyloxy. Halogen R1 is fluorine, chlorine, bromine or iodine, preferably chlorine.
Suitable fluorescent whitening agents are in particular the come of the formula 
the compound of the formula (2) being particularly preferred.
Preferably, the formulations according to the invention contain 3 to 15% by weight, in particular 5 to 12% by weight, of fluorescent whitening agents of the formula (1).
Suitable unmodified or modified polyvinyl alcohols are, for example, those compounds which are obtained by more or less complete saponification of polyvinyl acetate. In particular, they are polyvinyl alcohols having a saponification number between 10 and about 450. The saponification number (ester number) denotes the amount of KOH in mg which is consumed for hydrolysing 1 g of polyvinyl alcohol. Such polyvinyl alcohols are commercially available, for example under the names Mowiol and Polyviol.
Preferably, the formulations according to the invention contain 6 to 20% by weight, in particular 6 to 15% by weight, of an unmodified or modified polyvinyl alcohol. Suitable further additives are, for example, preservatives, e.g. 1,2-benzoisothiazolin-3-one or aldehydes, such as formaldehyde, acetaldehyde or glutaraldehyde, and antifreezes, solvents or antifoams. Small amounts of solvent are added, for example, in order to obtain completely clear solutions from formulations which are slightly turbid. Polyethylene glycols are excluded as additives.
To eliminate turbidity of the formulations according to the invention, it is also possible to carry out a clarified filtration at elevated temperature, for example at 50 to 70xc2x0 C.
The formulations according to the invention are obtained, for example, by thoroughly mixing the moist press cake or the dry powder of a fluorescent whitening agent of the formula (1) with an aqueous solution of an unmodified or modified polyvinyl alcohol and, if desired, further additives, if desired carrying out heating, for example to 30 to 80xc2x0 C., and mixing them with one another until a homogeneous distribution is achieved.
The solutions obtained have a relatively long shelf-life, for example 6 months, even at temperatures of about 0xc2x0 C. to 40xc2x0 C.
The formulations according to the invention are suitable for whitening paper materials in paper-making, for example from bleached chemical or mechanical pulp or mixtures thereof, and for whitening the unpigmented, but in particular pigmented, paper materials and coating slips usually used in the paper industry, including size press and film press applications.
The present invention therefore furthermore relates to the use of the formulations according to the invention for the fluorescent whitening of fibre dispersions in paper-making.